Copolymers of butadiene-1,3 hydrocarbons and other organic compounds



Patented Sept. 11, 1945 COPOLYMEBS OF BUTADlENE-L3 HYDRO- CARBONS AND OTHER ORGANIC M- POUNDS Waldo L. Semon, Silver Lake, Ohio, unis-nor to The B. F. Goodrich Company, New York; N. Y a corporation of New York No Drawing. sApplication January 24, 1942,

erial No. 428,083

14 Claims. (01. zoo-cs) This invention relates to the copolymerization carbon to oxygen double bond as in the strucof butadiene-l,3 hydrocarbons with other unture I saturated organic compounds and to the new a class of resinous or rubbery copolymers obtalnable thereby.

It is known that butadiene-1,3 hydrocarbons such as butadiene-1,3 and isoprene may be ccpolymerized with various unsaturated compounds which, in general, contain the group and no other carbon to carbon double bond, to form products which, depending on the relative proportions of the monomers utilized, are either rubbery or resinous in properties. For example, the copolymerization of butadiene-l,3 with a smaller amount by weight of methyl methacrylate yields a synthetic rubber while the copolymerization of butadiene-1,3 with a larger amount of methyl methacrylate yields a moldable synthetic resin.

I have now discovered that butadiene-l,3 hy

drocarbons, by which is meant butadiene-Lii and its homologs which polymerize in essentially the same manner such as isoprene, 2,3-dimethyl butadiene-1,3 and piperylene, may be copolymerized with other organic compounds of an entirely difierent class to form new rubbery or IGSlIIOLlS copolymers which are, for many purposes, superior to those heretofore known.

This new class of compounds which have been found to be copoiymerizabie with butadiene-1,3 hydrocarbons may be defined broadly as neutral organic compounds, composed of carbon, hydrogen and oxygen, wnich contain at least two carbon to carbon double bonds separated by at least one intervening atom so that they do not form a conjugated system, each of said double bonds occuring in a resinophoric group. The term resinophoric group is user herein in its ordinary sense to designate a chemical grouping in an organic compound which ubstantially increases the tendency of that compound to polymerize. The only resinophoric groups which may possibly be present in the structures of compounds of this class are groups in which a carbon to carbon double bond occurs at the end of. a carbon chain as in the structure and groups in which a carbon to carbon double bond occurs adjacent to (conjugated with) a Included in the above-defined class are neutral organic compounds composed of carbon, hydrogen and oxygen. such as esters, ketones and ethers, which contain at least two groups separated by at least one intervenin atom; similar compounds which contain at least one on c F group and at least one group separated therefrom by at least one intergroups separated by the ester linkage; 'acrylic and substituted acrylic esters of polyhydric alcohols such as glycol, glycerlne, diethylene glycol and trimethylene glycol and allyl, vinyl or 3-butenyl esters of alpha-beta unsaturated carboxylic acids such as acrylic, methacrylic, ethacrylic or crotonic acids, all of which contain at least one CH C group and at least one other carbon to carbon double bond which in this case not only has the structure but is at the same time conjugated with a carbon to oxygen double bond; divinyl, diallyl, and di-isopropenyl ketones, all or which contain at least two carbon to carbon double bondswhichareattheendoi'achainandare at the same time coniugated with the carbonyl group, and divinyl or diallyl ether or the polyvinyl ethers of po yhydric alcohols or phenols such as ethylene glycol. dieth'ylene glycol or hydroquinone, all of which containat least two CHFO groups separated by the ether linkage. The.

- from 60 to 80%, by weight of the mixture consists of a butadiene-1,3 hydrocarbon the copolymer formed by the polymerization of the mixtureisrubberyinnature and maybeusedas a synthetic rubber. If over 50%, preferably from 60 to 8096, by weig'ht of the mixture consists of the oxygen-containing monomer, however, the product is a resinous material useful as' a'molding composition. In any event it is obviously necessary to employ a substantial amount of each of the monomers in order to obtain a true copolymer, however, as little as 5% of the monomer present in the lesser amount may be employed. It is also sometimes desirable to include amonomer containinga' group and no other carbon to carbon double bond, such as styrene, acrylonitrile, methyl methacrylate, acrylic acid, vinyl chloride, vinylidene chloride or the like, in the mixture together with the oxygen-containing monomer and the butadiene-1,3 hydrocarbon in which case multipolymers of a variety of properties are formed by the polymerization. rmexample, the polymerization of a mixture containing 60% by weight of butadiene-l,3, 20% by weight of acrylonitrile and 20% by weight of vinyl crotonate yields a plastic synthetic rubber which, because of the presence of the acrylonitrile, is also somewhat oil resistant.

The polymerization of the above mixtures of monomers may be carried out by a number of different methods. For example, polymerization may be effected in homogeneous system by the application of heat. actinic li ht or pressure tothemixtureeitheraloneorinthepresenceof a solvent and either with or without the presence of a compound which initiates the po ymerisation reaction. It is'preferred, however, to carry out the polymerization in the form of an aqueous emulsion in the presence of a suitable emulsifying agent and a polymerization initiator.

' Emulsifylng asents which may be employed in I the emulsion polymerization process include fatty acid soaps such as sodium oleate, sodium palmitate or sodium stearate; aryl sulfonates such as sodium isopropyl naphthalene sulfonate: aliphatic sulfates such as sodimn lauryl sulfates and salts of high molecular weight organic bases assasra such as the hydrochloride of diethylaminoethyloleylamide and cetyltrimethylammonimn methy sulfate.

Polymerization initiators which may be used in either the homogeneous polymerization process or the emulsion polymerization process include benzoyl peroxide, potassium pe'rsuli'ate, hydrogen peroxide and other per-type oxygen containing compounds as well as other types of polymerization initiators such as diazoamino benzene and dipotassium diazomethane disulfonate. Those soluble in the monomers such as benzoyl peroxide are preferably used in the homogeneous process while those soluble in water such as hydrogen peroxide are preferably used in the emulsion process. Other substances which speedup the polymerization'reaction or which improve the quality of the products may also be present during the polymerization if desired.

The temperature and time necessary to bring about the copolymerization of the butadiene-L: hydrocarbon and the oxygen containing compound varies somewhat depending upon the method of polymerization and the substances present during the polymerization. In general it is necessary to use temperatures of about 100 C, or even higher when the homogeneous method of polymerization is used and to carry out the polymerization for 5-50 hours while with the emulsion polymerization process the temperature is preferably from 20-80 C. and the time of polymerization varies from 10 to 100 hours.

In order further to illustrate and clarify my invention the following examples are given although it is to be understood that the invention isnottobellmitedinanywaybythe details therein set forth.

Example 1 A mixture consisting of '15 parts by weight of butadiene-1,3 and 25 parts by weight of allyl crotonate are emulsified with 250 parts of a 2% aqueous solution of the hydrochloride of diethylaminoethyloleylamide, 2 parts by weight of benzoyl peroxide being present as an initiator. The resulting emulsion is allowed to polymerize, with constant agitation, for 2% days-at a temperature of 60 C. A latex like mass is thus obtained which, after the addition of 2 parts of phenyl beta naphthylamine, is coagulated with alcohol. A soft, plastic synthetic rubber which may be milled and otherwise processed in the same mannor as natural rubber is obtained. when compounded and vulcanized in the manner customary with natural rubber, this oopolymer yields vulcanizates of good elasticity and satisfactory tensile strength.

trample 2 Example 1 is repeated except that 50 parts by weight of butadiene-1,3 and 50 parts by weight of allyl crotonateare employed. The product is -a sticky, waxy, somewhat rubbery material which although not suitable as a synthetic rubber may be used in adhesivecompositions.

may

Seventy-five parts by weight of butadiene and I I V diallyl itaconate.

and vulcanized in the same manner asnatural rubber. Other diallyl esters which may be'substituted for diallyl adipate in this example with.

similar results include diallyl phthalate, dlallyl maleate, diallyl succinate, triallyl citrate and Example 4 A mixture of 75 parts of diallyl adipate, 25 parts of butadiene-1,3 and 5 parts of benzoyl peroxide is heated at 150 C. for about hours.

The product is a; white, tough, solid substance which is useful as a molding composition.

Example 5 tained.

Example 6 A mixture 0160 parts by weight of diallyl ketone and 40 parts by weight of butadiene-1,3 is po -merized in homogeneous system. A white solid resinous copolymer is obtained as the product.

Although I have specifically described only representative embodiments of my invention it will be apparent to those skilled in the art that many other materials, proportions and polymerization conditions may be employed without departing from the spirit and scope of my invention.

This application is a continuation-in-part of my copending application Serial No. 322,881, filed March 5, 1940.

,I claim:

1. The process which comprises polymerizing a mixture including from 5 to 95% by weight 01 a butadiene-1,3 hydrocarbon and from 5 to 95% by weight of a neutral organic compound composed of carbon, hydrogen, and oxygen, and containing an oxygen-containing structure selected from the class consisting of and -O, the said oxygen-containing structure being connected by each of its valences to a radical containing an oleflnic carbon to carbon double bond present in a group selected from the class consisting of 2. The process which comprises polymerizing in aqueous emulsion a mixture including from 5 to 95% by weight of butadiene-1,3 and from 5 to 95% by weight of a neutral organic compound composed of carbon, hydrogen, and oxygen, and containing an oxygen-containing structure selected from the class consisting of and -0, the said oxygen-containing structure being connected by each of its valences to a radical containing an oleflnic carbon double bond present in a group selected from the class consisting of 3. The process which comprises polymerizing a mixture including from 5 to 95% by weight of a butadine-L8 hydrocarbon and from 5 to by weight of a ketone composed of carbon, hydrogen, and oxygen. and containing the keto m n.

connected by each or its valences to a radical containing a oup.

4. The process which comprises polymerizing a mixture including from 5 to 95% by weight of a butadiene-1,3 hydrocarbon and from 5 to 95% by weight of an ester composed of carbon, hydrogen and owgen and containing the ester groupconnected, by the valence on the oxygen atom ,toaradical containinga cmr=c group and, by the valence on the carbon atom. to a carbon atom in turn connected by an oleflnic double bond to another carbon atom.

5. The process which comprises polymerizing in aqueous emulsion a mixture including from 50 to 95% by weight of butadiene-1,3 and from 5 to 50% by weight of an ester composed of carbon, hydrogen and oxygen and containing the ester growinl.

connected by the valence on the oxygen atom to a radical containing a group and, by the valence on the carbon atom, to a carbon atom in turn connected by an olennic double bond to another carbon atom.

6. The process which comprises polymerizing in aqueous emulsion a mixture containing butadiene-l,3 and an allyl ester of an alpha-beta unsaturated monocarboxylic acid, said mixture containing from 50 to 95% by weight of butadiene-1,3 and from 5 to 50% by weight of the said ester.

'7. The process which comprises polymerizing in aqueous emulsion a mixture containing at least 50% by weight of butadiene-1,3 and at least 5% by weight of allyl crotonate.

8. The process which comprises polymerizing a mixture including from 5 to 95% by weight of butadiene-1,3 and from 5 to 95% by weight of diallyl ketone.

9. A product prepared by the polymerization of a mixture including from 5 to 95% o! a butadiene-1,3 hydrocarbon and from 5 to 95% by weight of a neutral organic compound composed of carbon, hydrogen, and oxygen, and containing an oxygen-containing structure selected from the class consisting oi and -O, the said oxygen-containing structurebeing connectedbyeachoiitsvalencestoa the class consisting of containinga radical containing an oleiinio carbon to carbon double bond present in a group eelected from a and C- 10. A product prepared by the polymerization of a mixture including from 5 to 95% by weight of a butadiene-LS hydrocarbon and from 5 to 95% by weight of a ketone compoeed of carbon,

hydrogen, and oxygen; and containing the keto connected by each of its valence: to a radical assure hydrogen and oxygen and containing the ester connected,- by the valence on the oxygen atom, to a radical containing a group and, by the valence on the 'carbon atom, to a carbon atom in turn connected by an oleflnic double bond to another carbon atom.

12. A rubbery product prepared by the polymerization ot a mixture containing butadiene- 1,3 and an ally! ester of an alpha-beta unsaturated monocarboxylic. acid. said mixture containing from 5,0 to 95% by weight of butadiene- 1,3 and from 5 to by weight of said ester.

.13. A rubbery product prepared by the polymerization of a mixture containing atleaat 50% by weight of butadiene-l,3 and at least 5% by weight of allyl crotonafe.

14. A product prepared by the polymerization of a mixture including from 5 to by weight 01 butadiene-L3 and irom5 to 95% by weight 01 diallyl ketone.

' v I WALDO L. SEMON. 

